Production of sodium fluosilicate



7, 1948. c. OAKLEY, JR 2,447,359

'FRODUCTION OF SODIUM FLUOSILIGATE Filed Dec. 1, 1944 Patented Aug. 17, 1948 "I UNITED; STATES PATIENT] f;

. Llewellyn Cardiff Oakley, Jix, Tampa, Fla., as-.-, signor to Tennessee Corporati n,. New York,

'N.;Y,, a corporation of New York 7 Application December 1,1944, SerialNo. 566,094 a;

7 Claims. (c1.v 23-433 ;'li 'he present invention relates to the producproduced in superphosphatemanufacture and conversion of the fluorinecompoundsinto. fluosilicates. t Y f In the manufacture of superpho sphate, from phosphate rock by the treatment of the rock with sulphuric acid, gasesareevolved containing hydrofluoric acid, silicon tetrafluoride, and water vapor, together with other impurities, which "are toxic and cannotbe. permitted to escape into the atmosphere. 7. o

, Various methods have been devised and used in the recoveryoffluorine in usable form, such as sodium fluoride, sodium fluosilicate, hydrofluorieacid, artificial. cryo'lite, hydrofluosilicic acid, silicon fluoride, .andJoth'er compounds, but the methods have not proved entirely satisfactory for various reasons. Thelsu perphosp'hate gases have not been cleaned sufliciently to remove the last traces of noxiousconstituents, the yields ofthe fluorine compounds have. been low, due in most part to ineificient methods of conversion and recoverygandithe compounds obtained are contion of sodium. fluosilicate, in which .silicic ,acid

is separated .from the hydrofluosilicicacid prior to the reaction with a sodium sa'ltgto form' the' corresponding fluosilicate, the method of the present invention retain's', the silicicacid admixed with the .hy drofluosilicic acid during, the reaction with sodium chloride or other saltemployed'to form the fluosilicate, the .'s il'i cic acid being retained in vsuspension during the reaction, and in thesame ratio or. proportion to the hydrofluosilicic acid as exists in the scrubbertowers during the formation of the hydrofluosilicic acids; .The amount of. water employed in the-scrubber towers is controlledmoreover so as to produce a concentration of: the hydrofluosilicic; acid in the acid '2 I a slurry which will react with the b rine'o'r saltsolution; when added under the conditions hereinafter set forth to produce a crystal size of the fluosilicate which will readily settle in the acidfslurry While the silicic acidremains insusp'ensio'mthus permitting the separation of the fluosilicate salt from the acid slurry in a relatively pure state, without theiinclusion of silicic acid or otherim purities. o 1

By means of the method of the invention, hereinafter described in detail, the fluosilicatejas" so: dium vfluosilicate, .may be obtained substantially pure, containing from ..98.5 to 99.5 percent of the fluosilicate, with as little as from '0.3.. to 0.5% of sodium acid fluoride,and.0.5.% of mo'isture or less. The method of the inventionmakes-po ssible a yield of 'from 96 to 98% rec'overy'of the fluorine compounds in the superphosphate gases I in the form of hydrofluosilicic acid. Bylthe meth-'- od of the invention also the drying cost of the fluosilicate product is greatlyreducedover' the methods heretofore used, since the exclusion of silicic acidfr-om the fluosilicate crystals renders the drying of the product relatively easy and the maintenance of dryingile'quipm'ent is correspondingly reduced; During ,the drying operation, moreover, it is unnecessary to'add corrosion-inhibitingagents, such as sodium carbonate, to the fluosilicateproduct in order to protect the drying equipment during the drying operation, ashas heretofore been necessary in dryingsodiumfiuo silicatev and other metal fluosilicate salts produced by the methods heretofore employed.

. The present invention is based on the discovery that sodium fluosilicate of a highpurity may be produced from superphos'phate gases by controlling the amount of waterpassed into the scrubber.

towers so as to obtain an acid slurry of a. gravity of from, aboutfi to 10 Be. at F., ,by which the acid slurrywill contain jfrom 4.5 to 9.0%' of hydrofluosilicic acid, and thenreacting the slurry with brine or a saturated saltsolution at a definite controlled rate in amounts equivalentto twice up to nearly three times 'the theoretical amoun'tiof salt required for the reaction to'producesodium action liquid has become quiescent and before any substantial settlingfof the silicic acidhas taken place, thus permitting removal of the fluosilicate crystals from the remaining slurry.

It is an object of the invention to provide a new and improved method for the production of fluosilicates from the acid slurry obtained in the recovery of fluorine compounds from superphosphate gases by which a higher yield of fluosilicates may be obtained.

Another object of the invention is to provide a new and improved method for the recovery of fluorine compounds from superphosphate gases by which a substantially higher yield of such com pounds may be obtained than by methods hereto-' fore used.

A further object of the invention is to provide a new and improved method for the production of fluosilicates from the acid slurry obtained in the recovery of fluorine compounds from superphosphate gases which permits a reaction with a soluble salt in the acid slurry to form the corresponding fluosilicate without removal of silicic acid from the acid slurry.

is" also within the contemplation of the inverition" to provide a new and improved method {or the production of fluosilicates from the acid s'l ry obtained inthe recovery of fluorine cornunds from super phosphate gases by which fluotes of a higher purity than that obtainable by other prior methods may be produced.

"Moreover, it is an object of the invention to provide a method for the production of fluosilicates of high purity from the acid slurry prodi ced in the recovery'of fluorine compounds from superphcsphate gases by controlling the concentration oi the 'acid slurry with respect to the hydrofluosilicic acid and producing a reaction with a soluble salt of the metal, the fluosilicate of which isto be produced, in excess of the theoretical amount required for the reaction and ngthe saidirnetal salt at a rate to produce ii s licate crystals which will have a differential eettling'rate greater than that 'of silicic acid or other components of the solution so as to permit ,se 'aration of the said fluosilicate crystals from the reaction components. "F rthermore, it'is an object of the invention I vide a new and improved method f-or'the duction of riuosilicates from the acid slurry obta ned frcrn the scrubber towers in the treatof superphcsphate gases by which the fluosilicates may be obtained substantially free from s'l ica'o r silicic acid andsubstantiallyfree from o s u r a "I'hehiventi'on likewise contemplates the provision of a method by which sodium fluosilicate niay'be produced directly from the acid slurry cbta'ihed'inthe recovery of fluorine compounds from 'superphosphate gases and by which the drying costs in drying the product may be substantially reduced.

It'iss till another object of the invention to provide a' method for the production of fluo 's cates directly from the acid slurry obtained "the recovery of fluorine compounds from uperphosphate gases without the separation of 'silicic acid present in the acid slurry. In accordance with this object of the invention, the

cbn'centration of the acid slurry with respect to the hydrofluosilicic acid is controlled in the scrubber towers to within preferably from 6 to 8%of the hydrofluosilicic acid, or at least within L to 9% of'hydrofluosilicic acid, and a salt such as scdium chloride in solution, which is preferahly saturated, is added at a controlled rate, such asgallons per minute under ordinary comrnerc ial conditions, while the acid slurry'is agitated to retain the silicic acid in suspension during the reaction, by which fluosilicate crystals are formed of a size which Will settle rapidly in the reaction chamber as soon as the stirring or agitation is arrested and the reaction liquid becomes quiescent, after which the fluosilicate crystals may be substantially completely separated from the reaction cg nponents.

It is a further object (iii the invention to provide a new and improved method for the production of fluosilicates from the acid slurry obtained in the recovery of fluorine compounds from superphosphate gases in which silicic acid is permitted to remain in the presence of hydrofiuosilicic acid during reaction with a metal salt, by which the fluorosilicate compound may be separated by a differential settling rate, permitting the silicic acid to be substantially completely removed from the fluosilicate component by decantation or flotation in the presence of the settled layer of fluosilicate.

Still another object of the invention is'to providea method for the recovery of fluorine compounds from superphosphate gases without use of the ordinary 'slow process of filtration for the removal of silicic acid from the slurry so as to avoid loss of hydrofluosilicic acid through cc cl sion by the silicic acid, i w

With these and other objects in view, the inen on o ri e he a i usx w e n .0m,- bination of steps hereinafter described and more fieu r d ned n the a xe cl ms The method of the invention'is explained in connection with the accompanying drawing, in which the figure isa diagrammatic view in eleva-r n of a rm t a rat s in which t methvsi of the invention may be carried out.

Briefly stated, the invention involves the prodncticn oi fluosilicates,"and specifically sodium fluosilicate by first extracting fluorine compourids for superphosphate gases produced in the manuiacture of superphosphate by treatment of the said gases with water, as by spraying water there'- in, in definite predetermined proportions so as to react with silicon tetrafluoride in the gases to form hydroflu osilicic acid and silicic acid, and so as to absorb hydrofluoric acid in the gases, which reacts with silicic acid present to form additional brqroflu il eie a id- T mou o t r sprayed into the scrubber towers'is regulated so as to form an acid slurry containing preferably from 6 to 3 percent of hydrofluosilicic acid, or at least within the range of from i.5'to 9.0 percent e hrd -fleo il c c a i Th 'a id slurry is he treated with a soluble metal salt so as to form the metal fluosilicate desired, but Without the remove or s pa a io tthe si ic a id present, as has been the commercial practice heretofore, the e a alt olu i n m q sd. ha in a c ted exc s f the r quired am n e r r the reac ion to f rm e fluosi i ate nd b n d d at a predetermined rate during the, addition of at least half of the metal salt solution in order to, permit the formation of the desired Cr stal size .oi he flu s li ate wh c y b a at d i m he moth r uor o r a ni a d ur For the production of sodium fluosilicate from the acid slurry obtained from the scrubber towers, a sodium chloride solution is preferably used, the amount of sodium chloride theoretically required for the reaction with hydrofluosilicic acid being calculated based on the amount of the said acid i the Quan t 01 a sl rr t be treated A saturated solution of sodium chloride is then employed in excess of the theoretical amount required, the amount being preferably from 200 to during which the slurry is stirred or agitated so' as to retain the gelatinou'ssilicic acid in suspens'ion'. During theaddition of the sodium chloride solution, and while the silicic acid is-kept in suspension, crystals of sodium fiuosilicate are g'ra'dually'for'med, and'after the flrsthalf of the salt'solution has been added, the remainder of the solution may be admitted at substantially any desired rate, but preferably at least twice the speed employed in adding the main portion of the solution. After the total amount of the salt solu tion'h'a's beenadded, the stirring or agitation of the material in the reaction chamber is discone tinued, and the "reaction liquid is brought to quiescence by any suitable means, such as by the useof 'a paddle, and the crystals of the sodium fluosilicate are allowed to settle in the reaction chamber while'the 'silicic'acid remains in sus pension, which'requires generally about five min-- utes'." The supernatant layer of solution containing the s'ilicic'acid in suspension may then'be decanted or fdrawn off as by means of a syphon until only a relatively small proportion of the solution remains over the layer of sodium fluosilicatecrystals. The crystals may thenbe sepa-' rated irOmthe remaining layer of the reaction liquid, preferably 'by withdrawing the crystals from the reaction chamber through a narrow outlet into a'centrifugal separator, in which the crystals may be washed and spun nearly dry, after which the crystals may be dried in any suitable form of dryer so as to contain not more than 0.5 percent of moisture when the product is required forordin'ary commercial purposes. Referring more'in detail in the drawing, the numeral2 designates a pipe leading to the bot-' tom {of the scrubber tower 4 from the superphosphate 'den, not shown, by which the gas from the "reaction chamber containing hydrofluoric acid, silicon tetrafluoride and water vapor is passed-into the tower. In thetower 4, the gas passes upwardly to a passageway 6 which is connected to the top of the tower and from thence into the tower 8, and downwardly th'erethrough to a passageway in to the lower'end of a tower I2, in which the gas passes upwardly to passageway I4 connected to the top of the tower l2, and from thence to a tower l6, in which the gas passes downwardly until it'reaches an exit pipe l8 connected 'at'the lower end of the tower l6, through which thegasis exhausted to -the' atmosphere, being preferably expelled by means of an exhaust fan, not shown.-

n order to remove the last traces of hydrofluoric acid and silicon tetrafluoride from the gas in'the tower l6 before it is discharged into the atmosphere,'s'alt water, brine, or waste water containing sodium chloride, is pumped by means of a pump 20 through a pipe 22 and branch pipes 24, 26 and 28 into the tower l6, being discharged therein through spray nozzles 30, 32 and 34, connected respectively to pipes 24, 26 and 28, by which the salt water is sprayed into the tower at differentlevels. After passing to the bottom of the scrubber tower l6, the sprayed salt water containing dissolved or suspended material therein is collected ina catch basin 36 and is 'discharged to'waste through a separate overflow 38. In order to progressively absorb hydrofluoric acidand silicon tetrafiuoride from the gas passtower. correspondingly, water is pumped to the 6-. i-rig through towers 4, Band l2, fresh waterisiintroduced into the towers bymeans of sprays, be-

ing'pumped therein'by-means of a pump 46, pref-- branch pipes'54' and 56'from the pipe to the spray nozzles 58 and 60 in the tower 8, by which the gas passing downwardly in the tower is scrubbed in its passage therethrough' Water from the pipe 44 is also pumped through a'branch pipe 62 into the tower I2, in which the water is sprayed against the upwardly passing gas therein through spray nozzle 64. The water- I is pumped at high'pressure in order to provide a high degree of atomization and to insure a rapid cooling of the gases in passing through the towers, so as to obtain a substantially complete reaction inthe towers between the silicon tetrafiuoride carried by the gas and the water sprayed into thetowers. 1" It will be understood that the said silicon tetrafluoride and water react to produce hydrofluo silicic acid and silicic ac'id in accordance-with the following equation: f I 3SiF4+4H20=2H2SlFs+H4SiO4 The pump 40 is preferably mech-anically'or electrically connected to the phosphate, rock mixer" mechanism in a manner such that 'the pump'40 and the sprays 50, 52, 58, 60 and 64 are operated only when th sulfuric acid-phosphate rock mixer ls in operation. Thus when the said mixeris operated, the pump 46 is also. operated, and when the mixer is stopped, the pump .40 is also stopped.

.Iri the tower I2, additional sprays are employed in addition to the spray 64, the spray nozzles 66 and68 being connected to branch pipes "land .12 respectively, and are preferably operated. continuously from the plant fresh water/supply conducted to' the branch pi'pes'lfl and" aroma pipe 16 connected to supply pipe 42 as shown. The water conducted to sprays 66 and 68 may be fed at anysuitable pressure, .s'ay at35# per sq. in, and should be so arranged as to spraycontinuously. In the ordinary method of manufacture of 'superphosphate, small batches of phosphate rock and sulfuric acid are mixed and run into a den. When the den .is full, the mixing is stopped, the den opened and the superphosphate cut out and transported to storage. The den is then closed up and prepared for the next mixing. The major portion of the fluorine compounds are given off A during the mixing, while during the opening up or the den, cutting out, andpreparation of the den for the next charge, only small amounts of fluorine compounds are given off and drawn into the towers. For, thisrea'son, onlythe two sprays, 66 and 68 operate during the latter operations, to prevent dilution of the hydrofluosilicic acid.

The water spray passing downwardly in the scrubber towers 4, 8 and I2 discharge into a common sump 18, which connects the bottom of the towers 4, 8 and I2 and overflows to a pump sump 80. In order to keep the silicic acid in suspen sion in the acid'slurry in the sumps 18 and 80,'the slurry is pumped from the sump by means of a pump82 through a pipe 84 back to the sump 18 from which the slurry again overflows to the sump -80 and 'is re-circulated. The pipe 84 is pmvidediw itltai valve 8% so. that-thefiow through the piper mayrbe-cuttoff when: desired: Whom the": stump: 80 becomes; filled: with the i it i is: pumped; through.a;pipe:1in'e-88w through the-valve Mirtbastoragestank 92;.imwhichithe silicic acid maybe? maintained: in suspensioniin the-slurry by meansaofa a; stirrer: or. agitator Ma. The flow. ofa liquidz through the line; 88: may: bev cut oil? bymeans of; the: valve; 90;: while the: slurry is being"; re-circulztedf through: the; pipe: line.- 84 between: thesumps.l8a-ndi8tl.

'Ihecsilicimacid in:the'-slur ry.- storediin thertank 92. is kept. continuously; in. suspension inthe by theroperationof the stirrer'iflrs'o thatthe: slurry maybe drawn as; required from the; tanlc 92;: and: passed into: a reaction tank 96 through; a pipe" line 98= by: meansof a: pump I; A cutz-off valve I112 is. provided: in-th'e pipe: 98 so that flow through the line may be cut off as. de-- sired; When: a: measured: amount-of: the: acid. slurrstv has. been passedinto; the reaction; tank. 915; an: agitator. lflhnreferablyae two bladed stirrer ofi thelightningportable? type;,is put intooperation and the required quantity of brine;.0r= sat.- uratedf. sodium; chloride solutiom. asdetermined fromithe: amount of hydrofluosilicic acid present imtheereaction' tank to be treated, iSrthen'pa'SSed into the reaction tank 96 from a.-brine; measuring tank I06, the amount of sodium chloride employed being equivalent tofrcm 200 to 280% of the theoretical. amount, of the sodium chloride requireditd react with the fluosilicicaoid present, asmayr be: determined by calculating. the. said theoretical amount from the. following, equation:

A'fte!" the required amount of sodium chloride solution or' brine has i been .put into the tank l0 6i it is then allowedto how at a suitable rate; from the tank through a pipe line. lfl8,.th'erate*offl'ow being; controlled bysmeans of acut-ofi'va'llve' H0 therein', the brine or solution being, allowed? to flbwinto the slurry at" a: rate preferably of about 25 gallons per minute,. or other suitable rate; depending upon thetsize' of crystals desired;

The slurry in' the" reaction tank 196; containing. s'ilicic acid; hydrofluosilicic' acidqand sodium chloride; is vigorously'stirred'during the addition of the sodium chloride solution by means of an agitator I04; so. as to". break up any silicic acid agglomerates present .in'. the slurry; and" to thoroughly' disperse the sodiumchloride solution throughout" the liquid and. to accelerate the2reaction' between the. reacting ingredients.

When aboutone-l'ialf of the solution from the tankilflfi. has been passedii'nto the reaction tank 96; at the controlled rate, the remainder, of the salt'so'luticn may thenbe passedinto the. reaction tankatf'an increasedtsneed, such as 84" gallons. per minute',', fbr example,v with entirely satisfactory results:

The crystal size. of. the sodium. fluosilicate which'isformediin the reaction tank SFisdete-rlmined not only by therate of flow of theifirst half ormajor'portion ofthe brine or sodium chloride solution into. the. reaction .tank,v but also. by the rate of stirringduring. thetiniethat' the brineis passed into the tank, and'tov some extent also by thetemperature of the slurry duringthe reaction In ordinary. supeitphosphate. manufacture, the temperature of. theslurry. is. generally, substantiall'y constant; sothatilittle.variationin crystal size. of\ the. fluosilioate. crystals-.- will: bev produced b'y,- variations in. the. temperature or. the.- gas: Small .diiferences in. crystal. size obtainedaby the method oii'my invention may-beiaccounteddorrby changes in the rate of feed of-- the reacting; solu tion", particularly, during the:- time; that. the. first half: of thesolution' is-pa'ssed into the slurry. It will be understood: that: by thee additiom of. the: brine: orrsalt solution at rates s-ubstantially greata er than 25 gallons per minute;. the crystalss of, sodium fluosilicate which: are: formed: argsmaller; in: sizethan those-obtained'by the additionxof the brine'solution at arate of 25-gallons per'minuteor 'less, since-attthesslower rate: of= admission more; time is given: for the deveiopmenttofr the.- larger. size crystals-.-- The crystal size: of. the sodium. fiuosilicate isdependentalso; to.-somee extent; ,on the" concentration of, the hydrofiuosilicic acid: in the: slurry. It-has been found desirable ta cum-- trol the-proportionofiwater passing,to the scrub.=-- her. towers 4;v8'an'd 12, so'as toe-providei-aislunry having a gravity of from-Stu 10 Bzat 117;, so as" to contain. from; 4.5: to 9 percent ofhydrofiuosilicicacid, HzSiFe; and preferably from- Site 8* percent thereof. Concentrationslower: than about 4.5 percent'oi.hydrofiuosilicic. acid in-the slurry produce low sodiumfiuesilicate yields, and: concentrations higher: than about 9 percent. of hydrofluosilicicacid produce such aslarge volume of? silicic: acid per. unit volume of slurry that; the. sodium flucsilicate crystals will-not-settlesthrough the silicic acid in: the: succeeding; operation. next described.

Whenall of the brine in the-tank? I 06 a has been passed into the reaction. tank- 96; the agitator: IN: is stopped and: the slurry in the reaction tanlc may be calmedby, any suitable means; such as-by, theuse of a wooden paddle; for exampleyafteri whichcthe materialin the reaction tanlrisvallowed. to settle for a relatively short: period of= time; preferably about five minute'sin' ordinary commercial installations; The fluosilicate.- crystalswhich are. formed: settle= through. the mother liquoror suspensionain thetanls and may then be separated, from. the. supernatant liquid. by drawing Ofi l thersaid= liquid by.- meanswof a. syphon; forzex'ample: The: apnaratus may' be prepared foe drawing-off: the main portion" Ofi the-slurry con..- taining; silicio; acid: in, suspension; together with hydrochloric; acid: and: salt; by: ClOS-il'lg; the. valve H2. in th pipe: I M: and; passing, water. inta the syphon" l-lsrbys-opening theivalver M8-in the pipe IZO/ by, whicha-tell is passed into. the: flexible connection: or rubber hose.- I22. and; through: the syphon l'l fi'i until the syphon.is-fi1led.. I

The Syphon l lfids preferably mountedso as-to be adiustable in; position. and isspreierablm coumterhalanced by: means: of; a. weight.-. memben I24 whiehzis attached. to-a cable-orrrope I26 which passes over a. pulley member L28 and is-attached to the upper bend I30 of the syphon.v After the Syphon HBJha-s been" filledlwithwater from.- the pipe Mmthewa-lve; hi8. therein is:010sed andtthe syphon-l is.- then" raisedrby meanscf. the. cable I 26 into: a vnosition in. which the ,vertical..opening I37; atlthe en'diofthe-Syphon-isijust beiow the? surface of. theliquid: in-.the= reaction chamber: The-valve IH- inithe. pipe 1 W is-itheni opened" to: permit;. the supernatant liquid imthareaotionw chamben 951 to be drained oif or: passedto waste,, the syphon being gradually lowered in positioniaslthe liquid drainsscffi,. in:- order to keep the.=opening; IM of the: s-yghom below. the liquid; sur faceruntil-suhstagli'tially allaofi the liquid has: been drained; off and only a'nsmall amount of the waste: slurm is leftl-iw.the-reactionchamber above: the latter;v of fluosilicatecmstals:

. The: fluosilicater crystals are: their: drawn of! trifuge.

into acentrifuge I34 by opening a'valve I36 in 96. A'suitable. amount of water is then admitted to the bottom of the reaction tank 96 through a pipe I40 by opening a control valve I42 therein in order. to assist in'expelling or drawing off the 'fluosilicate crystals through the pipe I38 into the centrifuge I34.

All of-the' contents of th reaction tank "96.

except a small proportion of the original charge,

correspondin in ordinary size installations to approximately a six inch plug of the fluosilicate withholding the last portion or plug of the fluosilicate crystals in the outlet pipe I38, the residual silicic acid slurry is held back, which prevents it from contaminating the crystals in the cen- The plug or portion of the original charge which is held back in the pipe I38 may be conveniently retained in the reaction tank 96 so as to become a part of the next batch of acid slurry to be treated.

After the fluosilicat-e crystals, or sodium fluosilicate, have been passed into the centrifuge I34,

water may besprayed onto the crystals through a spray nozzle I44 attached to the pipe I46 through which water is passed, the flow of water therein being controlled -by means of a valve I48. Under ordinary conditions of commercial operation, the wash water will be sprayed overfications may be made in the method steps, as

will be apparent to those skilled in the art, without departing from the spirit or scope of the in- .vention as defined in the annexed claims. While it is preferred to separate the supernatant suspension ofsilicic acid from the settled layer of fiuosilicate crystals by syphoning ofi the supernatant liquid, in the manner above described in detail, it will be obvious that the mother liquor or supernatant suspension might b withdrawn from the crystals by decantation, or by other suitable means.

Having thus described the invention, what is claimed as new is:

1. A method for the production of sodium fluosilicate crystals from fluorine compounds contained in superphosphate gases which comprises spraying water in controlled amounts into the said superphosphate gases to form an acid slurry containing from about 6 to 8 percent of hydrofluosilicic acid together with silicicacidand other components, retaining the said silicic acid in suspension in the said slurry during the said spraying operation, passing the said acid slurry to areactionchamber while thesaid silicic acid remains in suspension therein, agitatin the said acid slurry in the said reaction chamber to main-.

10 tain-the silicic acid in-suspension in the liquid inthe said reaction chamber, gradually feeding a strong sodium chloride solution to thereaction chamber until a sufficient'amount thereof has been added to react with the hydrofluosilicic acid present to form sodium fluosilicate crystals and thereafter rapidly adding a substantial excess ofthe said sodium chloride solution while the silicic acid is retained in suspension, permitting the sodium fluosilicate crystals tosegregateinto a layer for a period of time insuflicient to cause settlingof the silicic acid in said liquid suspension,,and separating the said liquid suspension from the settled sodium fluosilicate crystal layer.

2. A method for the production of a metal fluosilicate from fluorine compounds in superphosphategases which comprises contacting said gases with a controlled amount of water to form an acid slurry containing between 4.5. and 9.0 percent of hydrofluosilicic acid together with silicic acid and continuously recirculatingthe said acid slurry during said contacting operation separately from the water contacting saidgases so as to maintain said silicic acid in suspension in said acid slurry, adding to said slurry at a controlled rate slowly enough to form metal fluosilicate crystals of suificient size to settle rapidly and substantially completely from the silicic acid in suspension, a solution of salt of said metal in excess of the amount required to react with the amount of hydrofluosilicic acid present in said acid slurry until the amount required for stoichiometrical reaction with the hydrofiuosilicic acid has been added and thereafter rapidly adding the excess of the said metal saltsolution, and maintaining the said silicic acid in suspensionin' the hydrofluosilicic acid in substantially the same stoichiometrical proportion to the hydrofluosilicic acid as when formed in said contacting reaction with water, permitting the reaction mixture to become quiescent to permit settling of metal fluosilicate crystals which have been'formed during a period in which the silicic acid remains in suspension and separating the said metal fluosilicate crystals and the said silicic acid suspension.

3. A method for the production of sodium fluosilicate crystals from superphosphate gases which comprises washing said gases with controlled amounts of Water sufilcient to form an acid slurry containing from 4.5 to 9.0 percent of hydrofluosilicic acid together with silicic acid formed in reaction between silicon tetrafluoride and water, recirculating the formedacid slurry during the said washing operation to maintain the already formed silicic acid in suspension, separating the formed acid slurry, adding to said slurry an excess of sodium chloride solution while maintaining the said silicic acid in suspension, the

said solution being added at a controlled rate slowly enough to form sodium fluosilicate crystals o'f-anefficient size, having rapid settling ratio,

, crystals from fluorine compounds carried by superphosphate gases which comprises 'washingithe csaiid gases with a controlled amount ;of water to iorm an acid slurry containing from 435 1:0 910 percent of'hy'drofiuos'ilici'c'acid together :with silicic-a'cid formed in the reaction of-water -with the said fluorine compounds, maintaining the said "silicic acid in suspension during'the formation'oi theacid slurry'by agitation, removing the-acid slurry formed and maintaining the said silicic acid "in suspension, treating the said slurry with -a substantially saturated "salt solution inexcess of the amount required for stoichiometric reaction with the hydrofluos'ilicic-acid'in t'heslurry by adding slowly at a controlled rate the amount of salt solution requiredfor'stoichio- =metric reaction to permit formation of relatively large flu'osilicate crystals which will settle while the said'silicic acid remains insusp'ens'ion' in the -sai'd s'lurry andad'ding the excess'oft'he-sal-t solution'at a relatively rapid rate during agitation of the slurry to 'retainthe-said silicic acid *in suspension, arresting the 'said agitation and permittlng the'said fluosilicate crystals to'settle'while the -silicic acid-remains in' suspension, syp'honing '"offt'he said silicic acid suspension except a I small "residual portion thereof, removing the settled fluosilicate crystalsthroug'h a narrow outlet exc nt *the 'sm'all -residual --portion'suflicient to form aplug to hold back the *said residual suspension -arid' washing the separated crystals.

admethodfor the production of sodiunrfluo- *s'il-i'cate crystals from fluorine compounds-insuperphosphate gases which comprises spraying water in controlled amounts intosaid-gases to forman acidslurry containing from about "7 to" 8 percent -*of "hydroflu'osilicic acid together with *Slllic"acidin th-ereaction of said fluorine compounds with said "water, separately recirculating thesaid ac-id -slurryduring the said washing operation,'=separatin'g-=a batch-of the said-acid slurry *for "treatment to --'form sodium iiluosilicate crys- "tals, stirring the said batch to retain siliCicacid in=suspension-therein, adding to thesai'd batch a "strong sodium chloride solution in excess of the amount required for stoichiometric reactionwith the hydrofluosilicioacid'present inth'e said batch, an amount oi thesaid sodium'chloride solution being first 2 added at a relatively slow controlled tate until the amount require'dior 'stoichiometr-ic reaction has' been added and the remainder of the said (sodium chloride solution being thereafter aiide'd=at a; more rapid'rate;maintaining the silicic acid distributed throughout thereactionliquid duringthe addition of-the Saidso'dium chloride =solutionto the said batch byagitation; arresting "the said a'gitation and'permittin'g the sodium fluosilicate crystals formed .to settle into a separate layer in the said suspension, .syphoning :Ofi "the *slliclc aci'd'suspension except arsmall residual portion thereon-removing the said layer of :sodium fiuosilicate crystals "through a restricted outlet eexcept a small residuallportionsufilcientto hold L'back the= saidiresidua'l suspension toprerrent ad- 'mixture with" the said removed crystals," returning the said residual 'sporti'ons'to thenext'batch 'o'f acidislurry to betreated,"washing'and centrifuging stheiriemoved sodium fluosilicatetcrystals"and -'.drying the=said crystals.

A"metho'd"for"th'e production offluosilicate "crystals from :fiuorine compounds carried by impel-phosphate gases which "comprises washing sthe fsaid ga'ses" progressively withwater sprays in controlled amounts to form 'anzacidfslurry containin'g from about ffifto 8rpercent'rof hydrofluotherein,

T2 :silicic acid together with s'ilicic "acid, sseparately :recirculating the saidacid slurry :during the said washing :foperation "to maintain the silicic acid in suspension -in ."the slurry, :separating a batch 5 of the said "slurry, i adding 'to the said 'batch at a -'controlled rate without removal of the .said :silicic acid'therefrom a substantiallyrsaturated solution of a "salt equivalent to "between .200 "and 280 percent of the amount thereof required-tome- :lO act-with the *hydrofiuosiliclc "acid present in athe said'batch'to form the-corresponding :fluosilicate, "a portionof the said salt-solution equivalentnsubstantially to "the amount of hydrofluosilicic acid present in the batch being added at-axcontrolled .15 rate" to permit the "formation of :large .fluosilicate crystals-and the remainder 'of said saltrsolution :being 'addedat a more :rapid rate, agitating-the batch slurryduring-the addition of the said :salt solution to'maintain the silicic acid-insusp'ension permitting the .fluosilicate crystals -.formedtoisettle into a separate layer while'the silicic acid remains in suspension, separating the said fiuosilicate crystals from-the said -siliciciacid suspension by removal of the major portion :of

- the said suspension from the said layer, washing and centrifuging .thessaid separated crystals-to purify the same and drying the crystalsto a low water content.

'7 A method for the production of sodium 111m- 1 silicate crystals .from fluorine compounds econin,. feedinga substantially saturated solution ,of

. sodium chloride ata rate 'between l5 :and 40 gallons pernninute into "the said batch until .an amount :of the sodium chloride substantially equivalenttothe .hydrofluosilicic acidiin thebatch has been added and thereafter feeding thersaid sodium chloride solutionat :about twice the first rate tuntilfrom v200 .to about 280 lpercentwof sodium chloride hasrbeen addedhpermittingrsodium .efluosilicate crystals -to segregate .into a layer for a period ,of time insufiicient =.to permit. settling-of the silicic acid in the suspension, syphoning off .the said .silicic acid suspension except a small residual .portion thereof, removing the settled ifluosilicate-crystals throughla narrow outletexcept .thei-small residual ,portion su'flicient .to-rform .a restriction .to hold .back the. said residual ,porltion of silicic acid suspension, centrifuging the separated sodium .fluos'ilicate .crystals, washing the said: crystals and drying .the product.

LLEWELLYN CARDIFF OAKLEY, JR.

REFERENCES CITED The following references are of recordfin the file of 'thispatent:

UNITED 'sTATEs PATENTS Number Name .Date

1,938,533 -Penfield Dec. 5,4933 2,369,791 Moore Feb. 20,1945 FOREIGN PATENTS ,Number Country Date Great Britain.. -Nov. -17, 19:27 

